Surface-treated substrate

ABSTRACT

A surface-treated substrate consisting essentially of a substrate having at least two treated surface layers wherein the first layer constituting the outermost layer among the treated surface layers is a layer obtained by treatment with a compound (I) capable of forming a surface having a contact angle of at least 70° against water and the second layer constituting an underlayer in contact with the outermost layer is a layer obtained by treatment with at least one reactive silane compound (II) selected from the group consisting of isocyanate silane compounds and hydrolyzable silane compounds.

FIELD OF THE INVENTION

The present invention relates to a substrate having a surface on whichwater drops scarcely attach or from which attached water drops caneasily be removed.

BACKGROUND OF THE INVENTION

Various substrates or various substrates having treated surface layersare used in various fields, and adverse effects brought about by waterto the surface of such substrates are problematic.

For example, in transportation equipments such as electric cars,automobiles, ships or aircrafts, the surface of an exterior part such asan outer panel, a window glass, a mirror or a display surface material,an interior part such as an instrument panel, or other articles, isdesired to be always clean. If rain drops, dusts or soils becomeattached, or moisture is condensed due to the temperature or humidity inthe air, on the surface of an article in a transportation equipment, theouter appearance will be impaired. If such is a surface which isdirectly visually observed or a surface which is directly touched by aperson, it may give an unpleasant feeling or may create a hygienicproblem. Further, such may bring about a deterioration of the inherentfunction which the article for a transportation instrument has.Especially in a case where the article for the transportation equipmentis an article for which transparency or see-through property is required(such as a window glass or a mirror), a deterioration of thetransparency or see-through property may mean that the purpose intendedby the article can not be attained, and may cause a serious accident.

A means to remove water drops (such as removal by wiping off or by meansof a wiper) may sometimes impart fine scratch marks on the surface.Further, such scratch marks may sometimes be widened by foreignparticles accompanying water drops. Furthermore, it is well known thatwhen moisture is attached to a glass surface, glass components arelikely to elute into the moisture, whereby the surface will be eroded,thus leading to so-called scorching. If the surface is strongly polishedor abraded to remove this scorching, a fine roughness is likely to form.At the see-through portion made of glass having substantial scorching ora fine roughness on its surface, its basic function is lowered, andscattering of light on its surface is substantial, whereby it tends tobe difficult to secure the field of view, and consequently there will bea problem in securing the safety.

Further, moisture is likely to hazardous by influence the surface of anarticle for a transportation instrument and to promote damage, soiling,yellowing or corrosion. Otherwise, it may induce a change in theelectrical characteristics, the mechanical properties or the opticalproperties of the article for a transportation equipment. The adverseeffects of this type brought by water are problematic not only in thefield of articles for transportation equipments but also in variousfields including articles for building or building decoration orarticles for electric or electronic equipments.

Under these circumstances, it is desired to impart to the substratesurface a characteristic such that water drops scarcely attach to thesubstrate surface or attached water drops can easily be removed (such acharacteristic will hereinafter be referred to simply as a water dropremoval property). Heretofore, to impart a water drop removal propertyto a surface, surface treating agents for direct application, such as asurfactant and a silicone oil made of silicone wax or organopolysiloxane, have been proposed.

However, such surface treating agents require pretreatment forapplication in many cases, and have a problem that nonuniformity inapplication is likely to occur. Further, the adhesive properties of suchtreating agents to the substrates are rather poor, whereby thedurability of the water drop removal property has been inadequate, andthe application range has been rather limited.

When the influence of moisture is taken into consideration, it isnecessary to establish a measure not only for various substrates to beproduced in the future but also for various substrates already beingused. In this case, it is necessary to impart the water drop removalproperty simply by direct application to various substrates at normaltemperatures. For example, when a case is taken into account whereinsuch treatment is to be applied to an automobile front glass alreadybeing used, it is not economical to replace the front glass of everyautomobile, or it is not practical to conduct baking after theapplication. Also from such an aspect, it is practically difficult tosolve the problems by the conventional treating agents.

The present invention has been accomplished in view of the aboveproblems. Namely, during the course of the research and study for atreating agent which is capable of solving the drawbacks inherent to theconventional treating agents, the present inventors have found atreating agent which is applicable to various types of substrates andwhich exhibits an excellent water drop removal property, and haveconfirmed that various substrates treated by such a treating agent aresuitable for use as substrates having a water drop removal property,particularly for transportation equipments or for building and buildingdecoration. The present invention has been completed on the basis ofthese discoveries.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide asubstrate having a water drop removal property, whereby such an effectlasts semipermanently with excellent abrasion resistance, chemicalresistance and weather resistance.

The above object can be accomplished by the present invention whichprovides a surface-treated substrate consisting essentially of asubstrate having at least two treated surface layers wherein the firstlayer constituting the outermost layer among the treated surface layersis a layer obtained by treatment with a compound (I) capable of forminga surface having a contact angle of at least 70° against water and thesecond layer constituting an underlayer in contact with the outermostlayer is a layer obtained by treatment with at least one reactive silanecompound (II) selected from the group consisting of isocyanate silanecompounds and hydrolyzable silane compounds.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now, the present invention will be described in detail with reference tothe preferred embodiments.

In the present invention, the compound (I) capable of forming a surfacehaving a contact angle of at least 70° against water (hereinaftersometimes referred to simply as the compound (I)) is a componentessential to provide the water drop removal property, and there is noparticular restriction as to the structure of the compound (I). However,the one having a reactive group is preferred, when the adhesion to thesecond layer which will be described hereinafter, is taken intoconsideration. Here, the reactive group means e.g. a functional groupsuch as a halogen group, an alkoxy group, an acyloxy group, analkoxy-substituted alkoxy group, an aminoxy group, an amide group, anacid amide group, a ketoxymate group, a hydroxyl group, a mercaptogroup, an epoxy group, a glycidyl group, an unsaturated hydrocarbongroup such as a vinyl group or an allyl group, or a carboxyl group, or afunctional group having atoms capable of forming a hydrogen bond (suchas oxygen atoms or nitrogen atoms).

The compound (I) has at least one hydrophobic organic group, since it isrequired to be a compound capable of forming a surface having a contactangle of at least 70° against water. As such a hydrophobic organicgroup, a long chain hydrocarbon group or an organic group havingfluorine atoms is, for example, suitable. A polyfluoroorganic group suchas a polyfluoroalkyl group or a polyfluoroalkylene group, isparticularly preferred. As such a polyfluoroorganic group, apolyfluoroorganic group as described hereinafter, particularly apolyfluoro hydrocarbon group, is preferred.

As a result of extensive studies, it has been found that an isocyanatesilane compound having at least one isocyanate group directly bonded toa silicon atom or a hydrolyzable silane compound having at least onehydrolyzable group directly bonded to a silicon atom and having theabove-mentioned hydrophobic organic group, is particularly effective asthe compound (I) in the present invention.

Hereinafter, "the reactive silane compound" is used to generallyrepresent both "the hydrolyzable silane compound" and "the isocyanatesilane compound" as described below. "The hydrolyzable silane compound"is a compound having at least one "hydrolyzable silane group" ("Si-X"where X is a hydrolyzable group) having at least one hydrolyzable groupbonded to a silicon atom. "The isocyanate silane compound" is a compoundhaving at least one "isocyanate silane group" (Si-NCO) having at leastone isocyanate group bonded to a silicon atom. "The reactive silanegroup" represented by "Si-Z" will be used as the general termrepresenting both of "the hydrolyzable silane group" and "the isocyanatesilane group".

It is possible to consider that "the isocyanate silane group" is onetype of "the hydrolyzable silane group" (namely, the isocyanate groupbonded to a silicon atom may be regarded as one type of a hydrolyzablegroup). However, in the present invention, the two are regarded as beingseparate. Namely, in the present invention, the isocyanate group bondedto a silicon atom is regarded as being not a hydrolyzable group (even ifthe isocyanate group is actually a hydrolyzable group).

Preferred as a reactive silane compound is a compound having 1 or 2reactive silane groups. As such a compound, more preferred is a compoundof the following formula (A) (hereinafter sometimes referred to ascompound A), a compound of the following formula (B) (hereinaftersometimes referred to as compound B), or in the case of the reactivesilane compound (II), a compound of the following formula (B) whereine+g+h is 0.

    (Z).sub.3-a-b (R.sup.1).sub.a (R.sup.2).sub.b Si-Y-Si(R.sup.3).sub.c (R.sup.4).sub.d (Z).sub.3-c-d                             (A)

wherein each of R¹, R², R³ and R⁴ which are independent of one another,is hydrogen or a C₁₋₂₁ organic group, Y is a bivalent organic group, Zis a reactive Silane group (i.e. an isocyanate group or a hydrolyzablegroup), each of a and b which are independent of each other, is aninteger of 0, 1 or 2, provided 0≦a+b≦2, and each of c and d which areindependent of each other, is an integer of 0, 1 or 2, provided 0≦c+d≦2,

    (R.sup.5).sub.e (R.sup.6).sub.g (R.sup.7).sub.h Si(Z).sub.4-e-g-h (B)

wherein each of R⁵, R⁶ and R⁷ which are independent of one another, ishydrogen or a C₁₋₂₁ organic group, provided that at least one of R⁵, R⁶and R⁷ is an organic group, Z is a reactive silane group (i.e. anisocyanate group or a hydrolyzable group), and each of e, g and h whichare independent of one another, is an integer of 0, 1 or 2, provided1≦e+g+h≦3.

The compound (I) is preferably a reactive silane compound having atleast one hydrophobic organic group. Particularly, among the compound ofthe above chemical formulas (A) and (B), preferred is a compound whereinat least one organic group is a hydrophobic group to obtain an excellentwater drop removal property. In this case, Z in the reactive silanegroup may be an isocyanate group or a hydrolyzable group.

On the other hand, the reactive silane compound (II) is a compound ofthe above formula (A) or (B), and compound B preferably includes acompound wherein e+g +h=0. This reactive silane compound (II) isdifferent from the compound (I) even when the compound (I) is a reactivesilane compound. It is desirable not only that the two reactive silanecompounds are different from each other, but also that the reactivesilane compound (II) is not a compound capable of forming a surfacehaving a contact angle of at least 70° against water. Accordingly, thereactive silane compound (II) preferably has no hydrophobic group,particularly no long chain hydrocarbon group or no organic group havingfluorine atoms. For example, the organic group of the compound A or B ispreferably an alkyl group having not more than 6 carbon atoms,particularly not more than 4 carbon atoms, or an alkylene group havingnot more than 8 carbon atoms, particularly not more than 6 carbon atoms.

However, these carbon numbers and hydrophobic properties are relativeand may vary depending upon the types of the compounds. Accordingly, solong as the first layer has a contact angle against water higher thanthe second layer, the second layer formed by the treatment with thereactive silane compound (II) may have a surface having a contact angleof 70° or higher against water. Namely, in certain cases, the reactivesilane compound (II) may be a compound capable of forming a surfacehaving a contact angle of at least 70° against water.

Now, the compound (I) will be described in further detail.

When the compound (I) is an isocyanate silane compound, this compound(hereinafter sometimes referred to as the compound (I-NCO)) is requiredto be a compound capable of forming a surface having a contact angle ofat least 70° against water. Namely, the contact angle against water ofthe surface treated with this compound (I-NCO) is required to be atleast 70°. The surface treated with the compound (I-NCO) is the surfaceof the second layer to which the compound (I-NCO) has been chemically orphysically bonded. Since an isocyanate group is reactive, the compound(I-NCO) is believed to be bonded to the surface of the second layerprimarily by a chemical reaction. Namely, in the bonded state, theisocyanate group is believed to be in a modified form. For example, anisocyanate group is believed to react with a silanol group on the glasssurface, or a silanol group formed by detachment of a hydrolyzable groupor an isocyanate group is considered to react.

It is believed that due to the reactivity of the isocyanate group or dueto the effect of the silicon atom directly bonded to the isocyanategroup, the compound (I-NCO) exhibits excellent surface properties suchas a water drop removal properly, abrasion resistance, chemicalresistance and weather resistance. As will be described hereinafter,such properties can further be improved by property selecting theorganic groups. Further, the number of isocyanate groups bonded to onesilicon atom is preferably at least two in view of the bonding propertyto the second layer.

Next, when the compound (I) is a hydrolyzable silane compound, thiscompound (hereinafter sometimes referred to as the compound (I-X)) isrequired to be a compound capable of forming a surface having a contactangle of at least 70° against water. Namely, the contact angle againstwater of the surface treated with this compound (I-X) is required to beat least 70°. The surface treated with the compound (I-X) is the surfaceof the second layer to which the compound (I-X) is chemically orphysically bonded. Since the hydrolyzable group is reactive, thecompound (I-X) is believed to be bonded to the surface of the secondlayer primarily by a chemical reaction. Namely, in the bonded state, thehydrolyzable group is believed to be in a modified form.

The hydrolyzable group in this compound (I-X) is a group directly bondedto a silicon atom. Such a hydrolyzable group includes, for example, ahalogen atom, an alkoxy group, an acyloxy group, an alkoxy-substitutedalkoxy group, an aminoxy group, an amide group, an acid amide group anda ketoxymate group. Preferred is a hydrolyzable group bonded to asilicon atom by means of an oxygen atom, such as an alkoxy group, analkoxy-substituted alkoxy group or an acyl group. The number of carbonatoms of such a hydrolyzable group is preferably at most 8, morepreferably at most 4. Most preferred is an alkoxy group having from 1 to4 carbon atoms.

It is believed that due to the reactivity of this hydrolyzable group orby the effect of a silicon atom to which the hydrolyzable group isdirectly bonded, the compound (I-X) exhibits excellent surfaceproperties such as a water drop removal property, abrasion resistance,chemical resistance and weather resistance. As described hereinafter,these properties can further be improved by properly selecting theorganic groups. The number of hydrolyzable groups bonded to one siliconatom is preferably at least two in view of the bonding property to thesecond layer.

The compound (I-X) may be used by itself, but may also be used as apartially hydrolyzed product obtained by hydrolysis. The partiallyhydrolyzed product of the compound (I-X) is a compound having e.g. asilanol group formed by partially hydrolyzing such a silane compound inwater or in an acidic aqueous solution, or a compound obtained bycondensation of at least two molecules by the reaction of such silanolgroups. As the acid, hydrochloric acid, acetic acid, sulfuric acid,phosphoric acid or phosphonic acid may, for example, be used.

These compounds (I-NCO) and (I-X) are preferably compounds capable offorming a surface having a contact angle of at least 70° against water,among reactive silane compounds A and B of the above described chemicalformulas. Such reactive silane compounds A and B (hereinafter sometimesreferred to as the compounds (I-A) and (I-B), respectively), arecompounds wherein R¹ to R⁷ are organic groups, and at least one of theseorganic groups is a hydrophobic group, or Y is a hydrophobic group. Allof the organic groups may of course be hydrophobic groups. The number ofZ groups is preferably at least two per silicon atom. A hydrophobicgroup is effective for the water drop removal property, and it isbelieved that the larger the number of Z groups, the more firmly thebond to the second layer becomes.

When each of R¹ to R⁷ is an organic group, such an organic group ispreferably a hydrocarbon group such as an alkyl group, an alkenyl group,a cycloalkyl group or an aryl group, a halogenated hydrocarbon groupsuch as a chloroalkyl group or a polyfluoroalkyl group, a(halogenated)hydrocarbon group having a hydroxyl group, an epoxy group,an amino group, a mercapto group, a carboxy group or other functionalgroup or a (halogenated)hydrocarbon group having an ester bond, an etherbond, a thioether bond, an imino bond, an amide bond, a urethane bond orother connecting bond in its carbon chain. Among them, the hydrophobicgroup may be a long chain hydrocarbon group or a polyfluoroalkyl groupas described hereinafter. The long chain hydrocarbon group is preferablyan alkyl group or an alkenyl group having from 7 to 20 carbon atoms. Asan organic group which is not a hydrophobic group, a lower alkyl groupi.e. an alkyl group having from 1 to 4 carbon atoms, is preferred.

More preferred as the compounds (I-A) and (I-B) are reactive silanecompounds having at least two fluorine atoms. Namely, in the case of thecompound (I-A), a compound is preferred wherein Y is a bivalent organicgroup having at least two fluorine atoms, otherwise at least one of R¹to R⁴ is a monovalent organic group having at least two fluorine atoms.Of course, both Y and at least one of R¹ to R⁴ may be organic groupshaving at least two fluorine atoms.

In the case of the compound (I-B), a compound is preferred in which atleast one of R⁵ to R⁷ is a monovalent organic group having at least twofluorine atoms. In such a case, the organic group having no fluorineatom is preferably a hydrocarbon group which is not a hydrophobic group.Further, the organic group having at least two fluorine atoms ispreferably bonded to the silicon atom by means of a carbon atom havingno fluorine atom (such as a methylene group).

When Y is a bivalent organic group having at least two fluorine atoms,such a group is preferably a polyfluoroalkylene group, apolyfluorooxalkylene group (the one wherein at least one ether bond ispresent in the carbon chain of the alkylene group) or apolyfluorothioxalkylene group (the one wherein at least one thioetherbond is present in the carbon chain of the alkylene group). Particularlypreferred is a bivalent organic group wherein the portions bonded toboth terminal silicon atoms are polymethylene chains (particularlydimethylene groups) and the intermediate portion is a perfluoroalkylenegroup or a perfluoroxalkylene group. The number of carbon atoms of suchY is a preferably from 6 to 30, particularly from 6 to 16.

When Y is not a bivalent organic group having at least two fluorineatoms, such a group is preferably an alkylene group, an oxalkylene groupor a thioxalkylene group. Its carbon number is preferably from 2 to 30,particularly from 2 to 12.

When any one of R¹ to R⁷ is a monovalent organic group having at leasttwo fluorine atoms, such a group is preferably a polyfluoroalkyl group,a polyfluorooxalkyl group or a polyfluorothioxalkyl group, or an organicgroup wherein any one of such groups and a hydrocarbon group such as analkylene group are bonded by an ester bond or other connecting bond asdescribed above (which organic group is bonded to a silicon atom at theother terminal of the hydrocarbon group). The polyfluoroalkyl group orthe polyfluorooxalkyl group is preferably the one wherein the terminalportions bonded to silicon atoms or the vicinities thereof are alkylenegroups (particularly dimethylene groups) and other portion is aperfluoroalkylene group.

The perfluoro moiety of a monovalent organic group is preferably aperfluoroalkyl group, a perfluorooxalkyl group or a perfluorothioxalkylgroup having at least 3 carbon atoms, particularly a perfluoroalkylgroup having from 3 to 16 carbon atoms.

Specific examples for such Y or R¹ to R⁷ will be presented in thefollowing specific examples for the compounds A and B. In the followingspecific examples, particularly preferred as the R_(f) group is apolyfluoroalkyl group having a perfluoroalkyl moiety of the formulaC_(n) F_(2n+1) C_(m) H_(2m) -- wherein n is an integer of from 3 to 12,and m is an integer of from 2 to 4. In the following specific examples,particularly preferred as the R_(f) group is C_(n) F_(2n+1) -- wherein nis an integer of from 3 to 16.

Specific examples of the compounds (I-A) and (I-B) will be shown below.However, the compounds (I-A) and (I-B) are not restricted to suchspecific examples. In the following chemical formulas, each of n and mis an integer of at least 1, R is an alkyl group, etc, R_(f) is apolyfluoroalkyl group, and R_(F) is a perfluoroalkyl group. In thesechemical formulas, R preferably has from 1 to 12 carbon atoms, and R_(f)is preferably an ethyl group having a perfluoroalkyl group at itsterminal. Z is an isocyanate group or a hydrolyzable group. ##STR1##

Two or more reactive silane compounds given above may be used incombination as the compound (I). However, it is advisable to avoid acombined use of an isocyanate silane compound and a hydrolyzable silanecompound, such as a combined use of a compound (I-NCO) and a compound(I-X), because the isocyanate group and the hydrolyzable group arelikely to react with each other whereby the life of the treating agenttends to be shortened.

As the compound (I), it is particularly preferred to use a compound(I-NCO). The compound (I-NCO) is superior to the compound (I-X) in thefilm-forming property, and it is also superior in the abrasionresistance of the film, whereby the water drop removal property will beprovided over a long period of time.

Further, it is preferred to use an organopolysiloxane together with thecompound capable of forming a surface having a contact angle of at least70° against water, in order to improve the effect of the surfacetreatment with the compound capable of forming a surface having acontact angle of at least 70° against water according to the presentinvention. As such an organopolysiloxane, silicone oil or a so-calledmodified silicone oil is suitable. Hereinafter such anorganopolysiloxane will be referred to as a compound C. This compound Cpreferably has polymer units of the following formula (C):

    [--SiR.sup.8 (CH.sub.3)--O--]                              (C)

wherein R⁸ is a C₁₋₁₆ organic group. This organic group R⁸ is preferablythe same organic group as described for R¹ to R⁷, particularly a loweralkyl group.

The compound C is effective for improving the water drop removalproperty and the abrasion resistance of the coating film formed by thetreatment with the compound capable of forming a surface having acontact angle of at least 70° against water, particularly with the abovecompound (I-A) or (I-B). The compound C may be added by itself to thecomposition for the surface treatment. Otherwise, it may be added afterhydrolysis with an acid such as sulfuric acid, hydrochloric acid oracetic acid. Further, the viscosity of the compound C is preferablydetermined taking a combination with other compound into consideration.Particularly preferred is the one having a viscosity at 25° C. of from0.5 to 1,000 centistrokes.

Now, specific examples of the compound C will be given. However, thecompound C is not restricted to such specific examples. In theseformulas, m, n, k and j are integers. ##STR2##

In the present invention, the composition for forming the first layerfor the treatment of the surface of the second layer contains a compoundhaving a contact angle of at least 70° against water, particularlypreferably the above-mentioned compound (I-A) or (I-B), as the essentialcomponent. The blending proportion of such a compound may be optional.When the compound C is incorporated, the proportion relative to othercomponents is optional, but the amount of incorporation is preferablyfrom 1 to 40% by weight. If the compound C is incorporated too much, notonly the abrasion resistance decreases, but also stickiness remains uponcontact with the surface. On the other hand, if it is too small, theabrasion resistance or the operation efficiency tends to be inadequatein some cases.

The compound C serves to improve the water drop removal property of thecoating film or to improve the durability of the film by the interactionwith other components (such as the above-mentioned compound (I-A) or(I-B)). The detailed mechanism is not known. However, it is believedthat the compound C interacts with other components in a complicated wayand consequently controls microscopic distributions of various organicgroups, particularly polar groups and ionic bonds present in thesurface, whereby a surface structure most suitable for the removal ofwater drops will be established.

The interaction of the molecules with such other selected components isbelieved to contribute to a remarkable improvement of the durability.Further, each compound having a contact angle of at least 90° againstwater is a substance having a low free surface energy, and a compound ina free state partially present in the coating film may move on theextreme surface layer so that the frictional resistance at the surfacewill be reduced. This is believed to be one of the factors for excellentabrasion resistance.

To the treating agent of the present invention, other compounds oradditives may be added depending upon the particular purpose. Theadditives, etc. may suitably be selected taking the reactivity andcompatibility with other components into consideration. For example, itis possible to incorporate super fine particles of various metal oxidessuch as silica, alumina, zirconia or titania or various resins. Further,a dye or pigment may also be added if tinting is required. The amount ofadditives is usually at a level of from 0.01 to 20% by weight based onthe total amount of other components, and an excessive addition is notadvisable, since such will reduce the water drop removal property orabrasion resistance of the present invention.

The above composition may directly be coated on the second layer as thecoating object by a manual application method. Otherwise, it may be usedin the form of a solution prepared by dissolving or diluting it with anorganic solvent. The total amount of various components contained in thesolution by means of such an organic solvent is determined taking intoconsideration the formability of the coating film (operationefficiency), the stability, the thickness of the coating film and theeconomical aspect, and it is usually within a range of from 0.1 to 30%by weight.

As the organic solvent, various organic solvents such as acetic acidesters, aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethersor alcohols, may be employed. However, when the compound A or B has anisocyanate group, a solvent having a reactive functional group (such asa hydroxyl group) is undesirable. Therefore. With respect to thecompound (I-NCO), alcohols are not desirable, but with respect to thecompound (I-X), there is no particular restriction. The diluting solventmay not be limited to one type, and two or more solvents may be used incombination as a mixture.

For the treatment of the surface of the second layer, no specialpretreatment is required. A coating film may be formed by applying theliquid containing the composition thus prepared, on the surface by ausual method, such as brush coating, casing, rotary coating, dip coatingor spray coating, followed by drying in air or in a nitrogen stream.

Excellent properties can be obtained simply by drying in air. However,for the purpose of increasing the drying rate, heating may be employedwithout any problem. The heating temperature is preferably at a level offrom 50° to 250° C., and the heating time is usually from 5 to 60minutes. If necessary, the heating temperature and time may bedetermined taking into consideration the heat resistance of thesubstrate.

The thickness of the first layer formed by this surface treatment is notparticularly limited. However, it is preferred to be very thin. Apreferred film thickness is at most 2 μm. The lower limit is a singlemolecular layer thickness.

Now, the reactive silane compound (II) and the second layer formed bytreatment therewith, will be described.

In the present invention, as the material for forming the second layer,the reactive silane compound (II) is used. The second layer constitutingan underlayer of the first layer serves to improve the durability of thefirst layer remarkably, and it also has an effect of improving theadhesion to the substrate. This second layer is usually formed on thesubstrate surface. However, there is no particular problem even when thesubstrate surface already has a vapor-deposited film, a sputtered filmor various films formed by e.g. a wet system.

The reactive silane compound (II) which forms the second layer, is acomound in which an isocyanate group is bonded directly to a siliconatom or a compound in which a hydrolyzable group is bonded directly to asilicon atom, like the above-mentioned compound (I-NCO) or (I-X), and itfirmly bonds to the first layer and to the underlayer (such as thesubstrate) by the reactivity of the isocyanate group and by the effectof the silicon to which isocyanate is directly bonded, or by the effectof the silicon to which the hydrolyzable group is directly bonded, andthus contributes to the improvement of the abrasion resistance.Accordingly, the larger the number of isocyanate groups or hydrolyzablegroups, per silicon atom, directly bonded to silicon atoms, the better.

When the essential component for forming the first layer is a reactivesilane compound, the group of the compounds selected from reactivesilane compounds and the group of compounds selected from reactivesilane compounds (II) for forming the second layer must not beidentical. Because if the two groups are identical, such is physicallymeaningless. However, the two groups of compounds selected from reactivesilane compounds may contain the same compound.

Preferred as the reactive silane compound (II) is a compound of theabove chemical formula (A) or (B) (hereinafter sometimes referred to asthe compound (II-A) or (II-B), respectively, but the compound (II-B)includes a compound wherein e+h+g=0). Preferably, it is a compound ofthe formula (A) or (B) other than the above compound (I).

When the reactive silane compound (II) is the compound (II-A) or (II-B),it may have at least one organic group bonded to a silicon atom. In sucha case, the organic group is preferably an organic group which is not anorganic group having a fluorine atom, more preferably a hydrocarbongroup. Most preferably, it is a lower alkyl group or an alkylene grouphaving not more than 6 carbon atoms. When the compound (I) has anorganic group containing a fluorine atom, the organic group of thecompound (II-A) or (II-B) may be the one having a low hydrophobic naturerelative thereto, and in some cases, it may be a long chain hydrocarbongroup.

Especially from the viewpoint of the adhesion to the first layer and tothe underlayer (such as the substrate), the larger the number ofisocyanate groups or hydrolyzable groups bonded to a silicon atom, thebetter. In the case of the compound (II-A), a compound of the formula(A) wherein a+b=0 and c+d=0, is preferred. In the case of the compound(II-B), a compound of the formula (B) wherein e+g+h=0, is preferred.

Specific examples of the compound in which an isocyanate group is bondeddirectly to silicon (hereinafter sometimes referred to as the isocyanatecompound (II-NCO)) among the reactive silane compounds (II), will begiven. However, the isocyanate silane compound (II-NCO) is not limitedto such specific examples. In the following formulas, p is an integer,preferably an integer of from 2 to 8. ##STR3##

Further, among the reactive silane compounds, the compound in which ahydrolyzable group is bonded directly to silicon (hereinafter sometimesreferred to as a hydrolyzable silane compound (II-X)) is preferably thecompound (II-B) (provided that Z is a hydrolyzable group, and e+h+g=0 isincluded) from the viewpoint of the adhesion to the substrate and to thefirst layer.

Specific examples of the hydrolyzable silane compound (II-X) will begiven below. However, the hydrolyzable silane compound (II-X) is notlimited to such specific examples.

Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane,tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane,tetra(secbutoxy)silane and tetra(t-butoxy)silane; trialkoxysilanes suchas methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane,methyltrimethoxyethoxysilane, ethyltriethoxysilane,vinyltrimethoxysilane, phenyltriethoxysilane,γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,chloromethyltrimethoxysilane, chloromethyltriethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane,glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane,β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane,γ-glycidoxypropyltrimethoxyethoxysilane,α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane,β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane,γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane,δ-glycidoxymethyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,(3,4-epoxycyclohexyl)methyltrimethoxysilane,(3,4-epoxycyclohexyl)methyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltripropoxysilane,β-(3,4-epoxycyclohexyl)ethyltributoxysilane,β-(3,4-epoxycycloehexyl)ethyltriethoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane,δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane andδ-(3,4-epoxycyclohexyl)butyltriethoxysilane; triacyloxysilanes such asmethytriacetoxysilane, vinyltriacetoxysilane, phenyltriacetoxysilane andγ-chloropropyltriacetoxysilane; triphenoxysilanes such asmethyltriphenoxysilane, γ-glycidoxypropyltriphenoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriphenoxysilane; dialkoxysilanes such asdimethyldimethoxysilane, phenylmethyldimethoxysilane,dimethyldiethoxysilane, phenylmethyldiethoxysilane,γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,methylvinyldimethoxysilane, methylvinyldiethoxysilane,glycidoxymethylmethyldimethoxysilane,glycidoxymethylmethyldiethoxysilane,α-glycidoxyethylmethyldimethoxysilane,α-glycidoxyethylmethyldiethoxysilane,β-glycidoxyethylmethyldimethoxysilane,β-glycidoxyethylmethyldiethoxysilane,α-glycidoxypropylmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,β-glycidoxypropylmethyldimethoxysilane,β-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldipropoxysilane,γ-glycidoxypropylmethyldibutoxysilane,γ-glycidoxypropylmethyldimethoxyethoxysilane,γ-glycidoxypropylethyldiethoxysilane,γ-glycidoxypropylethyldipropoxysilane,γ-glycidoxypropylvinyldimethoxysilane,γ-glycidoxypropylvinyldiethoxysilane andγ-glycidoxypropylphenyldiethoxysilane; diacyloxysilanes such asdimethyldiacetoxysilane; and diphenoxysilanes such asγ-glycidoxypropylmethyldiphenoxysilane.

In the present invention, as the reactive silane compound (II), it ispreferred to selectively use the isocyanate silane compound (II-NCO).The isocyanate silane group has a high reactivity as compared with thehydrolyzable silane group, and the reactivity of isocyanate groups toone another is low. Thus, it is excellent in the adhesion to thesubstrate. Further, when the second layer is formed, the majority ofisocyanate silane groups which have not reacted with the substrate areconverted to silanol groups (Si--OH), and many of them are reacted withthe first layer. (Whereas, in the case of hydrolyzable silane groups,the reactivity of the hydrolyzable silane groups to one another is high,whereby when the second layer is formed, there will be a less amount ofsilanol groups present on the surface as compared with the case wherethe isocyanate silane compound (II-NCO) is used.) Accordingly, theadhesion between the first layer and the second layer will be high, thusleading to excellent properties such as abrasion resistance anddurability. The most preferred reactive silane compound (II) istetraisocyanate silane.

As the treating agent to form the second layer of the present invention,it is advisable to use a solution or dispersion containing the reactivesilane compound (II) as an essential component. To this composition,other additives may be incorporated in addition to a solvent and adispersing agent. As the solvent, those described above with respect tothe compound (I) may be employed. However, with respect to the compound(II-NCO), alcohols are not suitable. The additives may, for example, bethe above-mentioned filler such as super fine particles of an metaloxide, a binder component and a surfactant. Their proportions maypreferably be as mentioned above. Their amounts may also preferably beas mentioned above.

For the surface treatment of the substrate, no special pretreatment isrequired. However, pretreatment may be conducted as the case requires.For example, acid treatment with e.g. diluted hydrofluoric acid orhydrochloric acid, alkali treatment with e.g. an aqueous sodiumhydroxide solution, or discharge treatment by e.g. plasma irradiation,may be conducted.

The second layer may be formed by applying a liquid composed of anorganic solvent containing the composition thus prepared, by a usualtreating method, such as brush coating, casting, rotary coating, dipcoating or spray coating, followed by drying in air or in a nitrogenstream at room temperature or under heating. Adequate drying can usuallybe conducted at room temperature. However, when the drying is conductedunder heating, the temperature and time may be determined inconsideration of the heat resistance of the substrate. However, heatdrying at a temperature for an extended period of time is likely toadversely affect the adhesion to the first layer.

There is no particular restriction as to the thickness of the secondlayer formed by this surface treatment. It may be very thin. A preferredfilm thickness is at most 2 μm like the case of the first layer.Further, the lower limit is a single molecular layer thickness. A toomuch thickness is undesirable from the economical viewpoint and from theviewpoint of the quality of appearance.

The thickness of each layer to be formed may suitably be controlled byadjusting the concentration of the composition of the liquid containingthe prepared composition, the coating conditions, the heatingconditions, etc. The first layer of the present invention has arelatively low refractive index, whereby low reflecting properties maybe imparted. If such an effect is desired, the thickness of the firstlayer may be adjusted to a thickness where an optical interference willoccur. Theoretically, the thickness of the coating film may be at leastthe thickness of a single molecular layer to obtain a water drop removalproperty. Taking an economical effect into consideration, the thicknessis preferably at most 2 μm, as mentioned above.

In the present invention, when the compound (I) is an isocyanatecompound having at least one polyfluoroorganic group, excellent waterrepellency, water drop removal property and suitable adhesion, can beachieved, even without providing a layer treated with the compound (II).However, in order to accomplish better adhesion, it is preferred toprovide an underlayer treated with the compound (II).

There is no particular restriction as to the substrate to which thepresent invention may be applied. For example, a metal, a plastic,glass, ceramic or other inorganic materials, an organic material, or acombination thereof (composite material, laminated material, etc.) maybe mentioned. Further, the surface of the substrate may, of course, bethe substrate surface itself, or may be the surface of a materialdifferent from the substrate surface, such as the coating surface ofe.g. a coated metal plate, or the surface of a surface-treated layer ofe.g. surface-treated glass. With respect to the shape of the substrate,it may not necessarily be a flat plate, and it may have an optionalshape depending upon the particular purpose, such as the one having acurvature over the entire surface or at a part thereof.

In the present invention, a particularly suitable substrate is asubstrate made of a transparent material such as glass or plastic, and asuitable article having such a substrate mounted to utilize thetransparency. Thus, the substrate of the present invention isparticularly suitable for articles for transportation equipments andarticles for buildings or building decorations.

Articles for transportation equipments may be exterior parts such asouter plates, window glasses, mirrors and display panels, and interiorparts such as instrument panels, of the transportation equipments suchas electric cards, buses, trucks, automobiles, ships or aircrafts, orparts or constituting elements to be used or already used in othertransportation equipments. Such an article may be composed solely of thesurface-treated substrate or may have the surface-treated substrateincorporated therein. For example, the former may be a window glass foran automobile, and the latter may be a back mirror for an automobile inwhich a glass mirror is incorporated.

The articles for transportation equipments include bodies, windowglasses, pantagraphs, etc. of electric cars, bodies, front glasses, sideglasses, rear glasses, mirrors, bampers, etc. of automobiles, buses ortrucks, bodies, window glasses, etc. of ships, and bodies, windowglasses, etc. of aircrafts.

With such substrates or articles, water drops on the surface will berepelled by the water drops removal property. Especially, in operation,due to the interaction with the receiving wind pressure, water dropsrapidly move on the surface and will not remain as water drops, wherebyany adverse effect which may otherwise be induced by moisture, can beeliminated. Especially in the application to a see-through portion suchas a window glass, it becomes easy to secure a viewing field due todissipation of water drops, thus leading to improvement of the safety ofa vehicle. Further, in an environment where water drops usually freeze,no freezing takes place, or even if freezing takes place, the frozendrops can readily be defrosted. Further, there will be no substantialdeposition of water drops, whereby the number of periodical cleaningoperations can be reduced. Besides, the cleaning operation is very easy,such being advantageous also from the protection of good appearance.

Further, the articles for buildings or building decorations may bearticles to be attached to buildings or articles already attached tobuildings, or articles for buildings which are not attached to buildingsbut which are used for the buildings, articles for buildings such asfurnitures or equipments, and base materials (such as glass plates)constituting such articles.

Specifically, they include window glass plates, window glasses, glassplates for roofs, various roofs including glass roofs, glass plates fordoors or doors having such glass plates installed, glass plates forpartitions, glass plates for green houses, or green houses having suchglass plates, transparent plastic plates to be used instead of glass,the above-mentioned various articles for buildings (window materials androof materials) having such plastic plates incorporated, wall materialsmade of ceramics, cement, metals or other materials, mirrors, furnituresand display shelves having such walls or mirrors, and glass forshowcases.

Such an article may be made of the surface treated substrate alone ormay be the one having the surface treated substrate incorporatedtherein. For example, the former may be a window glass plate, and thelatter may be a furniture in which a glass mirror is incorporated.

With such a surface treated substrate, water drops which are brought incontact with the surface are repelled due to the water drop removalproperty and scarcely attach to the surface, or if attached, the amountis small and the attached water drops can easily be removed. Further,even in an environment where water drops usually freeze, no freezingtakes place, or even if freezing takes place, the frozen drops canreadily be defrosted. Further, there will be no substantial depositionof water drops, whereby the number of periodical cleaning operations canbe reduced, and each cleaning operation will be very easy, and suchbeing advantageous also from the viewpoint of the protection of goodappearance.

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

The methods for evaluating various properties and the compounds used inthe Examples are as follows.

1. Water repellency

The contact angle of a water drop having a size of 1 mm in diameter wasmeasured. Measurements were made at five different points on thesurface, and the contact angle was represented by the average value.

2. Water drop removal property

A test sample was held vertically, and from a nozzle held at a distanceof 20 cm from the sample surface, water was sprayed over the entiresurface for about one hour, whereupon water drops remaining on thesurface were visually observed, and evaluated by the followingevaluation standards:

A: no water remained on the sample surface

B: water slightly remained on the sample surface

C: water substantially remained on the sample surface

D: water spread on the sample surface

3. Dropping angle

The dropping angle of a water drop having a size of 2 mm in diameter wasmeasured. Measurements were conducted at five different points on thesurface, and the dropping angle was represented by the average value.

4. Abrasion resistance

Tester: Taber rotary abrader (manufactured by Kabushiki Kaisha ToyoSeiki Seisakusho)

Test condition: Abrading ring H-22, load: 1 kg, number of rotations: 300times or 500 times.

The abrasion resistance test was conducted by the above test method, andthe water drop removal property after the test was evaluated. The numberof rotations being 300 times is designated as abrasion resistance 3, andthe number of rotations being 500 times is designated as abrasionresistance 5.

5. Weather resistance

A process comprising ultraviolet irradiation for 8 hours (70° C.) andhumidity exposure for 4 hours (50° C.) is regarded as one cycle, and theweather resistance test was conducted by 200 cycles.

The weather resistance test was conducted by the above method, and thewater removal property after the test was evaluated.

6. Boiling

A test sample was immersed in boiling water for one hour. The water dropremoval property after the test was evaluated.

7. Compounds used

(a) C₉ F₁₉ C₂ H₄ Si(OCH₃)₃

(b) (CH₃ O)₃ SiC₂ H₄ C₆ F₁₂ C₂ H₄ Si(OCH₃)₃

(c) C₉ F₁₉ C₂ H₄ Si(NCO)₃

(d) (OCN)₃ SiC₂ H₄ Si(NCO)₃

(e) Si(NCO)₄

(f) Si(OCH₃)₄

(g) CH₃ Si(OCH₃)₃

(h) CH₃ Si(NCO)₃

(i) C₈ H₁₇ Si(NCO)₃

(j) (CH₃)₂ Si(NCO)₂

(k) C₈ F₁₇ CH₂ CH₂ Si(NCO)₃

(l) (OCN)₃ SiC₂ H₄ C₆ F₁₂ C₂ H₄ Si(NCO)₃

(m) (CH₃)₃ SiO--[Si(CH₃)₂ --O--]_(n) --Si(CH₃)₃ (viscosity of 50centistokes)

(n) (CH₃ O)₂ (CH₃)SiC₂ H₄ C₆ F₁₂ C₂ H₄ Si(CH₃)(OCH₃)₂

(o) C₈ F₁₇ CH₂ CH₂ Si(OCH₃)₃

(p) Epoxy resin ("EP 827", tradename, manufactured by Yuka Shell EpoxyK.K.)

(q) Silica sol dispersed in methanol (solid content: 30 wt %,manufactured by Shokubai Kasei K.K.)

(r) Dimethylpolysiloxane having a viscosity of 50 centistokes (KF96,manufactured by Shinetsu Chemical Industries Company Limited)

(s) Modified diemthylpolysiloxane having a viscosity of 42 centistokesand having hydroxyl groups at both terminals (KF6001, manufactured byShinetsu Chemical Industries Company Limited)

(t) Modified dimethylpolysiloxane having a viscosity of 50 centistokesand having carboxyl groups (X-22-3710, manufactured by Shinetsu ChemicalIndustries Company Limited)

Preparation of treating agent 1

Into a three necked flask equipped with a stirrer and a thermometer,51.0 g of compound (a), 190.5 g of compound (b), 56.3 g of compound (f),6,020.0 g of 2-propanol and 14,500.0 g of 2-methyl-2-propanol were addedand stirred for one hour. Then, 22.2 g of magnesium perchlorate wasadded thereto, and the mixture was thoroughly stirred. While maintainingthe temperature of this solution at a level of not higher than 5° C.,67.4 g of a 1% hydrochloric acid aqueous solution was gradually dropwiseadded. After completion of the dropwise addition, stirring was continuedfor five days while maintaining the liquid temperature at a level of 25°C. to obtain treating agent 1.

Preparation of treating agent 2

Into a three necked flask equipped with a stirrer and a thermometer,45.0 g of compound (a), 180.5 g of compound (b), 46.3 g of compound (f),36.1 g of compound (q), 6.3 g of compound (t), 6,050.0 g of 2-propanoland 15,000.0 g of 2-methyl-2-propanol were added and stirred for onehour. Then, 25.2 g of magnesium perchlorate was added thereto, and themixture was thoroughly stirred. While maintaining the temperature ofthis solution at a level of not higher than 5° C., 70.4 g of a 1%hydrochloric acid aqueous solution was gradually dropwise added thereto.After completion of the dropwise addition, stirring was continued forfive days while maintaining the liquid temperature at 25° C. to obtaintreating agent 2.

Preparation of treating agent 3

Into a three necked flask equipped with a stirrer and a thermometer,50.0 g of compound (a), 182.5 g of compound (b), 50.3 g of compound (f),25.1 g of compound (g), 40.3 g of compound (q), 5,980.0 g of 2-propanoland 15,500.0 g of 2-methyl-2-propanol were added and stirred for onehour. Then, 23.4 g of magnesium perchlorate was added thereto, and themixture was thoroughly stirred. While maintaining the temperature ofthis solution at a level of not higher than 5° C., 74.2 g of a 1%hydrochloric acid aqueous solution was gradually dropwise added thereto.After completion of the dropwise addition, stirring was continued forfive days while maintaining the liquid temperature at 25° C. to obtaintreating agent 3.

Preparation of treating agent 4

Into a three necked flask equipped with a stirrer and a thermometer,75.5 g of compound (c) and 2,425.0 g of ethyl acetate were added. Whilemaintaining the liquid temperature of this solution at 25° C., stirringwas continued for one day to obtain treating agent 4.

Preparation of treating agent 5

Into a three necked flask equipped with a stirrer and a thermometer,50.0 g of compound (h), 15.0 g of compound (j), 10.2 g of compound (e),1,911.0 g of ethyl acetate and 535.4 g of toluene were added. Whilemaintaining the liquid temperature of this solution at 25° C., stirringwas continued for one day to obtain treating agent 5.

Preparation of treating agent 6

Into a three necked flask equipped with a stirrer and a thermometer,65.4 g of compound (i), 5.0 g of compound (d), 3.2 g of compound (r),1,900.0 g of isobutyl acetate and 500.0 g of methyl ethyl ketone wereadded. While maintaining the liquid temperature of this solution at 25°C., stirring was continued for one day to obtain treating agent 6.

Preparation of treating agent 7

Into a three necked flask equipped with a stirrer and a thermometer,35.1 g of compound (c), 35.4 g of compound (i), 3.5 g of compound (s)and 2,410.0 g of isobutyl acetate were added. While maintaining theliquid temperature of this solution at 25° C., stirring was continuedfor one day to obtain treating agent 7.

Preparation of treating agent 8

Into a three necked flask equipped with a stirrer and a thermometer,55.5 g of compound (e) and 2,775.6 g of isobutyl acetate were added.While maintaining the liquid temperature of this solution at 25° C.,stirring was continued for one day to obtain treating agent 8.

Preparation of treating agent 9

Into a three necked flask equipped with a stirrer and a thermometer,35.7 g of compound (e), 24.3 g of compound (d) and 2,775.6 g of ethylacetate were added. While maintaining the liquid temperature of thissolution at 25° C., stirring was continued for one day to obtaintreating agent 9.

Preparation of treating agent 10

Into a flask equipped with a stirrer and a thermometer, 78.5 g ofcompound (f), 1,020.2 g of methyl alcohol and 2,000.0 g of isopropylalcohol were added and stirred for one hour. While maintaining thetemperature of this solution at 5° C., 37.2 g of a 1% hydrochloric acidaqueous solution was gradually dropwise added thereto. After completionof the dropwise addition, stirring was continued for five days whilemaintaining the liquid temperature at 25° C. to obtain treating agent10.

Preparation of treating agent 11

Into a flask equipped with a stirrer and a thermometer, 75.0 g ofcompound (f), 10.9 g of compound (q), 1,203.5 g of methyl alcohol and2,000.0 g of isopropyl alcohol were added and stirred for one hour.While maintaining the temperature of this solution at 5° C., 35.5 g of a1% hydrochloric acid aqueous solution was gradually dropwise addedthereto. After completion of the dropwise addition, stirring wascontinued for five days while maintaining the liquid temperature at 25°C. to obtain treating agent 11.

Preparation of treating agent 12

Into a flask equipped with a stirrer and a thermometer, 56.3 g ofcompound (b), 29.4 g of compound (o) and 43.9 g of compound (f) wereadded and mixed, then 1,531.9 g of methyl alcohol and 7,000.0 g ofisopropyl alcohol were added, and 8.9 g of sodium acetate was furtheradded, and the mixture was stirred for one hour. While maintaining thetemperature of this solution at 5° C., 34.5 g of a 1% hydrochloric acidaqueous solution was gradually dropwise added thereto. After completionof the dropwise addition, stirring was continued for five days whilemaintaining the liquid temperature at 25° C. to obtain treating agent12.

Preparation of treating agent 13

Into a flask equipped with a stirrer and a thermometer, 23.0 g ofcompound (b), 10.8 g of compound (n), 30.0 g of compound (o), 22.4 g ofcompound (f) and 13.6 g of compound (p) were added and mixed, then1,708.9 g of methyl alcohol and 7,000.0 g of isopropyl alcohol wereadded, and the mixture was stirred for one hour. While maintaining thetemperature of this solution at 5° C., 23.6 g of a 1% hydrochloric acidaqueous solution was gradually dropwise added thereto. After completionof the dropwise addition, stirring was continued for five days whilemaintaining the liquid temperature at 25° C. to obtain treating agent13.

Preparation of treating agent 14

Into a flask equipped with a stirrer and a thermometer, 20.2 g ofcompound (i) and 1,980.0 g of butyl acetate were added. Whilemaintaining the temperature of this solution at 25° C., stirring wascontinued for one day to obtain treating agent 14.

Preparation of treating agent 15

Into a flask equipped with a stirrer and a thermometer, 19.9 g ofcompound (k) and 10.3 g of compound (l) were added and mixed, and 985.3g of ethyl acetate, 54.2 g of isopropyl alcohol and 456.3 g oftrichlorotrifluoroethane (R-113) were further added. While maintainingthe liquid temperature of this solution at 25° C., stirring wascontinued for five days to obtain treating agent 15.

Preparation of treating agent 16

Into a flask equipped with a stirrer and a thermometer, 9.8 g ofcompound (i), 2.4 g of compound (e) and 9.8 g of compound (k) were addedand mixed, and 970.0 g of butyl acetate, 35.5 g of isopropyl alcohol and200.0 g of trichlorotrifluoroethane (R-113) were added thereto. Whilemaintaining the liquid temperature of this solution at 25° C., stirringwas continued for one day to obtain treating agent 16.

Preparation of treating agent 17

Into a flask equipped with a stirrer and a thermometer, 19.9 g ofcompound (k) and 10.3 g of compound (l) were added and mixed, and 985.3g of ethyl acetate, 54.2 g of isopropyl alcohol and 456.3 g oftrichlorotrifluoroethane (R-113) were added. 1.8 g of compound (m) and0.2 g of sulfuric acid were added. While maintaining the liquidtemperature of this solution at 25° C., stirring was continued for fivedays to obtain treating agent 17.

EXAMPLE 1

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 8 and withdrawn therefrom at a rate of 5 cm/min,followed by drying at room temperature. This test piece was dipped in asolution of treating agent 1 and withdrawn therefrom at a rate of 5cm/min, followed by heating at 200° C. for 30 minutes to obtain a sampletest piece. This test piece was evaluated, and the results are shown inTable 1.

EXAMPLE 2

The test and evaluation were conducted in the same manner as in Example1 except that treating agent 8 in Example 1 was changed to treatingagent 9. The results are shown in Table 1.

EXAMPLE 3

The test and evaluation were conducted in the same manner as in Example1 except that treating agent 1 in Example 1 was changed to treatingagent 2. The results are shown in Table 1.

EXAMPLE 4

The test and evaluation were conducted in the same manner as in Example1 except that treating agent 1 in Example 1 was changed to treatingagent 3. The results are shown in Table 1.

EXAMPLE 5

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 8 and withdrawn therefrom at a rate of 5 cm/min,followed by drying at room temperature. This test piece was dipped in asolution of treating agent 4 and withdrawn therefrom at a rate of 5cm/min, followed by drying at room temperature to obtain a sample testpiece. This test piece was evaluated, and the results are shown in Table1.

EXAMPLE 6

The test and evaluation were conducted in the same manner as in Example5 except that treating agent 4 in Example 5 was changed to treatingagent 5. The results are shown in Table 1.

EXAMPLE 7

The test and evaluation were conducted in the same manner as in Example5 except that treating agent 4 in Example 5 was changed to treatingagent 6. The results are shown in Table 1.

EXAMPLE 8

The test and evaluation were conducted in the same manner as in Example5 except that treating agent 4 in Example 5 was changed to treatingagent 7. The results are shown in Table 1.

EXAMPLE 9

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 1 and withdrawn therefrom at a rate of 5 cm/min,followed by heating at 200° C. for 30 minutes to obtain a sample testpiece. This test piece was evaluated, and the results are shown in Table1.

COMPARATIVE EXAMPLE 1

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 5 and withdrawn therefrom at a rate of 5 cm/min,followed by drying at room temperature to obtain a sample test piece.This test piece was evaluated, and the results are shown in Table 1.

COMPARATIVE EXAMPLE 2

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 8 and withdrawn therefrom at a rate of 5 cm/min,followed by drying at room temperature to obtain a sample test piece.This test piece was evaluated, and the results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Water         Waterdrop removal property                                      repellency    Initial Abrasion  Weather                                       Initial stage stage   resistance 5                                                                            resistance                                                                           Boiling                                ______________________________________                                        Example 1                                                                             108       A       A       A      A                                    Example 2                                                                             108       A       A       A      A                                    Example 3                                                                             106       A       A       A      B                                    Example 4                                                                             105       A       A       A      B                                    Example 5                                                                             115       A       A       A      A                                    Example 6                                                                             112       A       B       A      B                                    Example 7                                                                             116       A       A       A      A                                    Example 8                                                                             115       A       A       A      A                                    Example 9                                                                             108       A       B       A      B                                    Compara-                                                                              115       A       B       A      B                                    tive                                                                          Example 1                                                                     Compara-                                                                               43       D       D       D      D                                    tive                                                                          Example 2                                                                     ______________________________________                                    

EXAMPLE 10

The test piece prepared in Example 5 was dipped in the reagent asidentified in Table 2 for 24 hours, and it was then withdrawn andimmediately cleaned. Then, the change of the outer appearance and thewater drop removal property of this test piece were confirmed. Theresults are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                      Change of the                                                                              Waterdrop                                          Reagent       outer appearance                                                                           removal property                                   ______________________________________                                        Methanol      No change    A                                                  Acetone       No change    A                                                  Toluene       No change    A                                                  Water         No change    A                                                  1% sulfuric acid                                                                            No change    A                                                  aqueous solution                                                              1% sodium     No change    A                                                  hydroxide                                                                     aqueous solution                                                              Commericially No change    A                                                  available                                                                     cleaning agent                                                                Carbon        No change    A                                                  tetrachloride                                                                 Gasoline      No change    A                                                  ______________________________________                                    

EXAMPLE 11

The test piece prepared in Example 1 was dipped in the reagent asidentified in Table 3 for 24 hours, and it was withdrawn and immediatelycleaned. Then, the change of the outer appearance and the water dropremoval property of this test piece were confirmed. The results areshown in Table 3.

                  TABLE 3                                                         ______________________________________                                                      Change of the                                                                              Waterdrop                                          Reagent       outer appearance                                                                           removal property                                   ______________________________________                                        Methanol      No change    A                                                  Acetone       No change    A                                                  Toluene       No change    A                                                  Water         No change    A                                                  1% sulfuric acid                                                                            No change    A                                                  aqueous solution                                                              1% sodium     No change    A                                                  hydroxide                                                                     aqueous solution                                                              Commericially No change    A                                                  available                                                                     cleaning agent                                                                Carbon        No change    A                                                  tetrachloride                                                                 Gasoline      No change    A                                                  ______________________________________                                    

EXAMPLE 12

Coating on the surface of a laminated front glass for an automobile wasconducted in the same manner as in Example 5 to form a coating film. Thelaminated front glass thus obtained was mounted on an automobile. Thisautomobile was subjected to a running test for 4 hours every day for onemonth, and the deposition of dust and stain on the surface of the frontglass, or in a rainy day, the deposition of water drops, was visuallyobserved every day.

As a result, no deposition of dust or stain, or no formation of fur dueto deposition of water drops, was observed, or even when observed, itwas readily removed by gently wiping it off with a tissue paper.Further, at the time of raining, water drops on the surface wererepelled and moved away swiftly by the interaction with the windpressure due to running, whereby the viewing field was secured withoutusing a wiper. Further, in a running test in an environment (0° C. to-5° C.) where water drops deposited on a non-treated laminated frontglass would freeze, or moisture in air would condense to form frost on afront glass, no formation of frost on the front glass was observed.

In a severer low temperature environment (-10° C. to -15° C.), formationof frost on the front glass was observed, but defrosting was quick, andthere was a substantial difference as compared with the non-treatedfront glass.

EXAMPLE 13

The running test was conducted in the same manner as in Example 12except that the laminated front glass in Example 12 was changed to aside glass or a rear glass, whereby the same effects as in Example 12were confirmed.

EXAMPLE 14

The running test was conducted in the same manner as in Example 12except that the laminated front glass in Example 12 was changed to aside mirror, whereby the same effects as in Example 12 was confirmed.

EXAMPLE 15

The laminated front glass of an automobile which was used under a normalcondition for 5 years, was polished with calcium carbonate, washed withwater and dried for one hour. To the laminated front glass thus cleaned,treating agent 9 was applied with a cotton cloth. After drying for 10minutes, treating 4 was then applied with a cotton cloth, followed bydrying for 10 minutes. Using this automobile, a running test wasconducted in the same manner as in Example 12, whereby the same effectsas in Example 12 were confirmed.

EXAMPLE 16

Coating on the surface of a window glass for building was conducted inthe same manner as in Example 5 to form a coating film. The window glassthus obtained was mounted on a house. The deposition of dust and stainon the surface of this window glass, or in a rainy day, the depositionof water drops, was visually observed every day.

As a result, no deposition of dust or stain, or no formation of fur dueto deposition of water drops, was observed, or even when observed, itwas readily be removed by gently wiping it off with a tissue paper.Further, at the time of rain, water drops on the surface were repelledand fell off, and especially when strong wind blew, water drops werereadily moved off by the interaction with the wind pressure, whereby theviewing field was secured. Further, in a test under an environment (0°C. to -5° C.) where water drops deposited on a non-treated window glasswould freeze, or moisture in air would condense to form frost on awindow glass, no formation of frost on the window glass was observed.

In a severer low temperature environment (-10° C. to -15° C.), formationof frost on the window glass was observed, but the defrosting was quick,and there was a substantial difference as compared with the non-treatedwindow glass.

EXAMPLE 17

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 10 and withdrawn therefrom at a rate of 11 cm/min,followed by heating at 80° C. for 10 minutes. This test piece was leftto stand at room temperature for 30 minutes, and then it was dipped in asolution of treating agent 12 and then withdrawn therefrom at a rate of11 cm/min, followed by heating at 200° C. for 30 minutes to obtain asample test piece. This test piece was evaluated, and the results areshown in Table 4.

EXAMPLE 18

The test and evaluation were conducted in the same manner as in Example17 except that treating agent 12 in Example 17 was changed to treatingagent 13. The results are shown in Table 4.

EXAMPLE 19

The test and evaluation were conducted in the same manner as in Example17 except that treating agent 10 in Example 17 was changed to treatingagent 17. The results are shown in Table 4.

EXAMPLE 20

The test and evaluation were conducted in the same manner as in Example17 except that in Example 17, treating agent 10 was changed to treatingagent 11, and treating agent 12 was changed to treating agent 13. Theresults are shown in Table 4.

EXAMPLE 21

The test and evaluation were conducted in the same manner as in Example17 except that in Example 17, the heating after dipping in treatingagent 10 was changed from 80° C. for 10 minutes to 300° C. for 30minutes. The results are shown in Table 4.

COMPARATIVE EXAMPLE 3

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 12 and then withdrawn therefrom at a rate of 11 cm/minto obtain a sample test piece. This test piece was evaluated, and theresults are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Water         Waterdrop removal property                                      repellency    Initial Abrasion  Weather                                       Initial stage stage   resistance 3                                                                            resistance                                                                           Boiling                                ______________________________________                                        Example 17                                                                            108       A       A       A      A                                    Example 18                                                                            108       A       A       A      A                                    Example 19                                                                            108       A       A       A      A                                    Example 20                                                                            108       A       A       A      A                                    Example 21                                                                            108       A       B       B      B                                    Compara-                                                                              108       A       B       A      A                                    tive                                                                          Example 3                                                                     ______________________________________                                    

EXAMPLE 22

The test piece prepared in Example 17 was dipped in the reagent asidentified in Table 5 for 24 hours, and then it was withdrawn andimmediately cleaned. Then, the change of the outer appearance and thewater drop removal property of this test piece were confirmed. Theresults are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                      Change of the                                                                              Waterdrop                                          Reagent       outer appearance                                                                           removal property                                   ______________________________________                                        Methanol      No change    A                                                  Acetone       No change    A                                                  Toluene       No change    A                                                  Water         No change    A                                                  1% sulfuric acid                                                                            No change    A                                                  aqueous solution                                                              1% sodium     No change    A                                                  hydroxide                                                                     aqueous solution                                                              Commericially No change    A                                                  available                                                                     cleaning agent                                                                Carbon        No change    A                                                  tetrachloride                                                                 Gasoline      No change    A                                                  ______________________________________                                    

EXAMPLE 23

Two surface-treatment layers were formed on the surface of the laminatedfront glass for automobile in the same manner as in Example 17. Thelaminated front glass thus obtained was mounted on an automobile. Thisautomobile was subjected to a running test for 4 hours every day for onemonth. The deposition of dust and stain on the surface of the frontglass, or in a rainy day, the deposition of water drops, was visuallyobserved every day.

As a result, no deposition of dust or stain, or no formation of fur dueto deposition of water drops, was observed. Even when observed, it wasreadily removed by gently wiping it off with a tissue paper. Further, atthe time of rain, water drops on the surface were repelled and readilymoved away by an interaction with the wind pressure due to running,whereby the viewing field was secured without using a wiper. Further, ina running test in an environment (0° C. to -5° C.) where water dropsdeposited on a non-treated laminated front glass would freeze, ormoisture in air would condense to form frost on a front glass, noformation of frost on the front glass was observed.

In a severer low temperature environment (-10° C. to -15° C.), formationof frost on the front glass was observed, but defrosting was quick, andthere was a substantial difference as compared with the non-treatedfront glass.

EXAMPLE 24

A running test was conducted in the same manner as in Example 23 exceptthat the laminated front glass in Example 23 was changed to a side glassor a rear glass, whereby the same effects as in Example 23 wereconfirmed.

EXAMPLE 25

A running test was conducted in the same manner as in Example 23 exceptthat the laminated front glass in Example 23 was changed to a sidemirror, whereby the same effects as in Example 23 were confirmed.

EXAMPLE 26

Coating on the surface of a glass plate for building was conducted inthe same manner as in Example 17 to form a coating film. The glass platefor building thus obtained, was mounted on a building. This window glasswas subjected to an exposure test for one month, and the deposition ofdust or stain on the surface of the window glass, or in a rainy day, thedeposition of water drops, was visually observed every day. As a result,no deposition of dust or stain, or no formation of fur due to depositionof water drops, was observed, or even if observed, it was readilyremoved by gently wiping it off with a tissue paper.

Thus, the cleaning operation of the window glass was substantiallysimplified. Further, at the time of rain, water drops on the surfacewere repelled, and no spread of water was observed, whereby the viewingfield was easily secured. Further, in a rainy day with a strong wind,water drops were readily moved away by the interaction with the windpressure, whereby the viewing field was more readily secured.

Further, in an exposure test in an environment (0° C. to -5° C.) wherewater drops deposited on a non-treated window glass would freeze, ormoisture in air would condense to form a frost on a window glass, noformation of frost on the surface of the window glass was observed. In aseverer low temperature environment (-10° C. to -15° C.), formation offrost on the window glass was observed, but defrosting due to atemperature rise was quick, and there was a substantial difference ascompared with the non-treated window glass.

EXAMPLE 27

An exposure test was conducted in the same manner as in Example 26except that the glass plate for building was changed to a heat-rayreflection glass plate for building ("Sun Lux SS8" manufactured by AsahiGlass Company Ltd). As a result, the same effects as in Example 26 wereconfirmed.

EXAMPLE 28

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in a solutionof treating agent 10 and withdrawn therefrom at a rate of 11 cm/min,followed by heating at 80° C. for 10 minutes. The test piece therebyobtained was left to stand at room temperature for 30 minutes. Then, itwas dipped in a solution of treating agent 14 and withdrawn therefrom ata rate of 11 cm/min, followed by heating at 150° C. for 30 minutes toobtain a sample test piece. This test piece was evaluated, and theresults are shown in Table 6.

EXAMPLE 29

The test and evaluation were conducted in the same manner as in Example28 except that treating agent 14 in Example 28 was changed to treatingagent 15. The results are shown in Table 6.

EXAMPLE 30

The test and evaluation were conducted in the same manner as in Example28 except that treating agent 14 in Example 28 was changed to treatingagent 16. The results are shown in Table 6.

EXAMPLE 31

The test and evaluation were conducted in the same manner as in Example28 except that treating agent 14 in Example 28 was changed to treatingagent 17. The results are shown in Table 6.

EXAMPLE 32

The test and evaluation were conducted in the same manner as in Example28 except that treating agent 10 in Example 28 was changed to treatingagent 11. The results are shown in Table 6.

EXAMPLE 33

The test and evaluation were conducted in the same manner as in Example28 except that in Example 28, treating agent 10 was changed to treatingagent 11, and treating agent 14 was changed to treating agent 15. Theresults are shown in Table 6.

EXAMPLE 34

The test and evaluation were conducted in the same manner as in Example28 except that in Example 28, treating agent 10 was changed to treatingagent 11, and treating agent 14 was changed to treating agent 16. Theresults are shown in Table 6.

EXAMPLE 35

The test and evaluation were conducted in the same manner as in Example28 except that in Example 28, treating agent 10 was changed to treatingagent 11, and treating agent 14 was changed to treating agent 17. Theresults are shown in Table 6.

EXAMPLE 36

The test and evaluation were conducted in the same manner as in Example28 except that in Example 28, the heating after the dipping in treatingagent 10 was changed from 80° C. for 10 minutes to 300° C. for 30minutes. The results are shown in Table 6.

EXAMPLE 37

A glass plate of 10 cm×10 cm (thickness: 3 mm) was dipped in treatingagent 16 and withdrawn therefrom at a rate of 11 cm/min to obtain asample test piece. This test piece was evaluated, and the results areshown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Dropping      Waterdrop removal property                                      angle         Initial Abrasion  Weather                                       Initial stage stage   resistance 3                                                                            resistance                                                                           Boiling                                ______________________________________                                        Example 28                                                                            57        A       A       B      B                                    Example 29                                                                            60        A       A       A      A                                    Example 30                                                                            58        A       A       A      B                                    Example 31                                                                            62        A       A       A      B                                    Example 32                                                                            55        A       A       B      B                                    Example 33                                                                            61        A       A       A      A                                    Example 34                                                                            59        A       A       A      B                                    Example 35                                                                            61        A       A       A      B                                    Example 36                                                                            60        A       B       B      B                                    Example 37                                                                            60        B       B       C      D                                    ______________________________________                                    

EXAMPLE 38

The test piece obtained in Example 30 was dipped in the reagent asidentified in Table 7 for 24 hours, and it was withdrawn and immediatelycleaned. Then, the change of the outer appearance and the water dropremoval property of this test piece were confirmed. The results areshown in Table 7.

                  TABLE 7                                                         ______________________________________                                                      Change of the                                                                              Waterdrop                                          Reagent       outer appearance                                                                           removal property                                   ______________________________________                                        Methanol      No change    A                                                  Acetone       No change    A                                                  Toluene       No change    A                                                  Water         No change    A                                                  1% sulfuric acid                                                                            No change    A                                                  aqueous solution                                                              1% sodium     No change    A                                                  hydroxide                                                                     aqueous solution                                                              Commericially No change    A                                                  available                                                                     cleaning agent                                                                Carbon        No change    A                                                  tetrachloride                                                                 Gasoline      No change    A                                                  ______________________________________                                    

EXAMPLE 39

Coating on the surface of a laminated front glass for an automobile wasconducted in the same manner as in Example 30 to form a coating film.The laminated front glass thus obtained was mounted on an automobile.This automobile was subjected to a running test for 4 hours every dayfor one month, and the deposition of dust or stain on the surface of thefront glass, or in a rainy day, the deposition of water drops, wasvisually observed every day.

As a result, no deposition of dust or stain, or no formation of fur dueto deposition of water drops, was observed, or even if observed, it wasreadily removed by gently wiping it off with a tissue paper. Further, atthe time of rain, water drops on the surface were repelled and readilymoved away by the interaction with the wind pressure due to running,whereby the viewing field was secured without using a wiper. Further, ina running test in an environment (0° C. to -5° C.) where water dropsdeposited on a non-treated laminated front glass would freeze, ormoisture in air would condense to form frost on a front glass, noformation of frost on the front glass was observed.

In a severer low temperature environment (-10° C. to -15° C.), formationof frost on the front glass was observed, but defrosting was quick andthere was a substantial difference as compared with the non-treatedfront glass.

EXAMPLE 40

A running test was conducted in the same manner as in Example 39 exceptthat the laminated front glass in Example 39 was changed to a side glassor a rear glass, whereby the same effects as in Example 39 wereconfirmed.

EXAMPLE 41

A running test was conducted in the same manner as in Example 39 exceptthat the laminated front glass in Example 39 was changed to a sidemirror, whereby the same effects as in Example 39 were confirmed.

EXAMPLE 42

Coating of treating agents on the surface of a glass plate for buildingwas conducted in the same manner as in Example 30 to form two layers ofcoating films. The glass plate for building thus obtained, was mountedon a building. This window glass was subjected to an exposure test forone month, and the deposition of dust or stain on the surface of thewindow glass, or in a rainy day, the deposition of water drops, wasvisually observed every day.

As a result, no deposition of dust or stain, or no formation of fur dueto deposition of water drops, was observed, or even if observed, it wasreadily removed by gently wiping it off with a tissue paper. Thecleaning operation of the window glass was substantially simplified.Further, at the time of rain, water drops on the surface were repelled,and no spread of water was observed, whereby the viewing field waseasily secured. Further, in a rainy day with a strong wind, water dropswere readily moved away by the interaction with the wind pressure,whereby the viewing field was more readily secured.

Further, in an exposure test in an environment (0° C. to -5° C.) wherewater drops deposited on a non-treated window glass would freeze, ormoisture in air would condense to form frost on a window glass, noformation of frost on the surface of the window glass was observed. In aseverer low temperature environment (-10° C. to -15° C.), formation offrost on the window glass was observed, but defrosting due to atemperature rise was quick, and there was a substantial difference ascompared with the non-treated window glass.

EXAMPLE 43

A exposure test was conducted in the same manner as in Example 42 exceptthat the glass plate for building in Example 42 was changed to aheat-ray reflection glass plate for building ("Sun Lux SS8",manufactured by Asahi Glass Company Ltd.) As a result, the same effectsas in Example 42 were confirmed.

EXAMPLE 44

With respect to test pieces prepared in Examples 1, 5, 7, 9, 19, 29, 32,35 and Comparative Example 1, the following evaluation of the abrasionresistance was conducted, and the results are shown in Table 8.

Abrasion resistance

Tester: Reciprocation-type scratch tester (manufactured by K.N.T. K.K.).

Testing conditions: A flannel cloth was reciprocated under a load of 1kg, and the number of reciprocations where the contact angle of waterwas maintained to be 90°, was examined.

                  TABLE 8                                                         ______________________________________                                                     Number of                                                                     reciprocations                                                   ______________________________________                                        Example 1      15,000                                                         Example 5      33,000                                                         Example 7      25,000                                                         Example 9      15,000                                                         Example 19     10,000                                                         Example 29     28,000                                                         Example 32     15,000                                                         Example 35     18,000                                                         Comparative     5,000                                                         Example 1                                                                     ______________________________________                                    

The substrate of the invention or an article having the substratemounted, exhibits excellent effects as is evident from the foregoingExamples. Namely:

1. It is excellent in the water drop removal property and is free fromdeposition of dust, stain or water drops, or free from formation of furdue to such deposition, or even when formed, such fur can readily beremoved, whereby adverse effects which may otherwise be induced by watercan be prevented, and it is possible to simplify the cleaning operation.

2. It is excellent in maintaining the water drops removal property, andis capable of maintaining such a condition semi-permanently.

3. It is excellent in chemical resistance, and can be applied at aregion along sea coast or at a region where sea water is directly incontact. Thus, it is applicable in wide range of fields.

4. It requires no special pretreatment, whereby the economical advantageis substantial.

Especially, it has a long lasting water drop removal property even at anormal temperature treatment.

5. The water drop removal property is most suitable for use in the fieldof transportation equipments and in the field of building and buildingdecorations.

The above effects can not be expected with conventional materials, andthe present invention is expected to be applied in an area where theconventional materials could not practically be used.

What is claimed is:
 1. A surface-treated substrate consistingessentially of a substrate having at least two different treated surfacelayers wherein the first layer constituting the outermost layer amongthe treated surface layers is a layer obtained by treatment with acompound (I) containing at least one Si--NCO group capable of forming asurface having a contact angle of at least 70° against water, and thesecond layer constituting an underlayer in contact with the outermostlayer is a layer obtained by treatment with at least one reactive silanecompound (II) selected from the group consisting of isocyanate silanecompounds and hydrolyzable silane compounds.
 2. The substrate accordingto claim 1, wherein the substrate is made of glass.
 3. The substrateaccording to claim 1, wherein the substrate is a part for atransportation equipment.
 4. The substrate according to claim 1, whereinthe substrate is a part for a building material or building decoration.5. The substrate according to claim 1, wherein the compound (I) is areactive silane compound of the following formula (A) or (B) wherein atleast one organic group is a polyfluoroorganic group:

    (Z).sub.3-a-b (R.sup.1).sub.a (R.sup.2).sub.b Si--Y--Si(R.sup.3).sub.c (R.sup.4).sub.d (Z).sub.3-c-d                             (A)

wherein each of R¹, R², R³ and R⁴ which are independent of one another,is hydrogen or a C₁₋₂₁ organic group, Y is a bivalent organic group, Zis an isocyanate group or a hydrolyzable group, each of a and b whichare independent of each other, is an integer of 0, 1 or 2, provided0≦a+b≦2, an each of c and d which are independent of each other, is aninteger of 0, 1 or 2, provided 0≦c+d≦2,

    (R.sup.5).sub.e (R.sup.6).sub.g (R.sup.7).sub.h Si(Z).sub.4-e-g-h (B)

wherein each of R⁵, R⁶ and R⁷ which are independent of one another, ishydrogen or a C₁₋₂₁ organic group, provided that at least one of R⁵, R⁶and R⁷ is an organic group, Z is an isocyanate group or a hydrolyzablegroup, and each of e, g and h which are independent of one another, isan integer of 0, 1 or 2, provided 1≦e+g+h≦3, each of reactive silanecompound of the formula (A) and (B) containing at least one Si--NCOgroup.
 6. The substrate according to claim 5, wherein thepolyfluoroorganic group is an organic group having a C₃₋₂₁perfluoroalkyl moiety or a C₂₋₁₆ perfluoroalkylene moiety.
 7. Thesubstrate according to claim 5, wherein the hydrolyzable group is ahydrolyzable group selected from the group consisting of a halogen atom,an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group,an aminoxy group, an amide group, an acid amide group and a ketoxymategroup.
 8. The substrate according to claim 1, wherein the compound (I)is an isocyanate silane compound having at least one polyfluoroorganicgroup.
 9. The substrate according to claim 1, wherein the reactivesilane compound (II) is a compound selected from the group consisting ofa compound of the following formula (A), a compound of the followingformula (B) and a compound of the formula (B) wherein e+g+h is 0:

    (Z).sub.3-a-b (R.sup.1).sub.a (R.sup.2).sub.b Si--Y--Si(R.sup.3).sub.c (R.sup.4).sub.d (Z).sub.3-c-d                             (A)

wherein each of R¹, R², R³ and R⁴ which are independent of one another,is hydrogen or a C₁₋₂₁ organic group, Y is a bivalent organic group, Zis an isocyanate group or a hydrolyzable group, each of a and b whichare independent of each other, is an integer of 0, 1 or 2, provided0≦a+b≦2, and each of c and d which are independent of each other, is aninteger of 0, 1 or 2, provided 0≦c+d≦2,

    (R.sup.5).sub.e (R.sup.6).sub.g (R.sup.7).sub.h Si(Z).sub.4-e-g-h (B)

wherein each of R⁵, R⁶ and R⁷ which are independent of one another, ishydrogen or a C₁₋₂₁ organic group, provided that at least one of R⁵, R⁶and R⁷ is an organic group, Z is an isocyanate group or a hydrolyzablegroup, and each of e, g and h which are independent of one another, isan integer of 0, 1 or 2, provided 1≦e+g+ h≦3.
 10. The substrateaccording to claim 9, wherein the hydrolyzable group is a hydrolyzablegroup selected from the group consisting of a halogen atom, an alkoxygroup, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxygroup, an amide group, an acid amide group and a ketoxymate group. 11.The substrate according to claim 1, wherein the reactive silane compound(II) is a reactive silane compound having no polyfluoroorganic group.12. The substrate according to claim 1, wherein the reactive silanecompound (II) is an isocyanate silane compound.
 13. The substrateaccording to claim 1, wherein the compound (I) is an isocyanate silanecompound having at least one polyfluoroorganic group, and the reactivesilane compound (II) is an isocyanate silane compound having nopolyfluoroorganic group.
 14. The substrate according to claim 13,wherein the isocyanate silane compound having no polyfluoroorganicgroup, is tetraisocyanate silane.
 15. The substrate according to claim1, wherein the compound (I) is an isocyanate silane compound having apolyfluoroorganic group, and the reactive silane compound (II) is ahydrolyzable silane compound.
 16. The substrate according to claim 15,wherein the hydrolyzable silane compound is a hydrolyzable silanecompound having no polyfluoroorganic group.
 17. The substrate accordingto claim 1, wherein the first layer is a layer obtained by treatmentwith a composition comprising the compound (I) and anorganopolysiloxane.
 18. The substrate according to claim 17, wherein theorganopolysiloxane is an organopolysiloxane having repeating units ofthe following formula (C) and a viscosity of from 0.5 to 1,000centistrokes at 25° C.:

    [--SiR.sup.8 (CH.sub.3)--O--]                              (C)

wherein R⁸ is a monovalent C₁₋₁₆ organic group.
 19. The substrateaccording to claim 1, wherein the treated surface layers are prepared insuch a manner that the substrate surface is treated with a compoundcontaining an isocyanate silane compound (II) to form the second layer,and then the second layer surface is treated with a compositioncontaining the compound (I) to form the outermost layer.
 20. Asurface-treated substrate having a treated surface layer formed bytreatment with an isocyanate silane compound having at least onepolyfluoroorganic group.